Calcium ammonium lactate

ABSTRACT

Crystalline calcium ammonium lactate dihydrate, a constituent formed from fermented ammoniated condensed whey, and is useful as a nutrient for ruminant animals.

This is a division of U.S. application Ser. No. 109,480 filed Jan. 4,1980 which in turn is a continuation-in-part of U.S. application Ser.No. 093,162 filed Nov. 13, 1979, now abandoned.

The present invention relates to solidified forms of fermentedammoniated condensed whey (hereinafter called "FACW") and methods ofmaking same. The invention is also related to calcium ammonium lactate,a constituent formed in that method which assists in solidification ofFACW and which is a useful nutrient for ruminant animals.

BACKGROUND OF THE INVENTION

FACW is a liquid feed supplement which is manufactured by fermentingwhey with lactic acid producing bacteria, such a Lactobacillusbulgaricus, in the presence of ammonia. The fermentation of wheyconverts carbohydrate to lactic acid, which is neutralized by ammonia toform ammonium lactate. The fermentation also multiplies the bacteria,which consequently provide additional protein. The fermentation product,which typically will contain 6 to 16% solid matter, is then concentratedby evaporation typically to a solids content of 40 to 68%.

Since ruminant animals can utilize ammonium salts as a source ofnitrogen for synthesis of protein, FACW is useful as a feed supplementfor them. As a liquid, it can be applied to other ration components,such as shelled corn silage, oats, or oil seed meals. It would beuseful, however, to have FACW available in a solid form, for example,for use on farms which are not equipped to use liquid feed supplements.

Protein supplement and mineral blocks, pellets or other feeds processedvia binding are normally made with expensive presses using binders suchas molasses, lignin sulfonate or bentonite. These methods often requiresteam conditioning of the meal prior to pressing and the application ofhigh pressure (2000 to 3000 psi). The current invention, whilecompatible with this equipment, is a basic improvement in that thisequipment is not necessary and little or no pressure or heat need beapplied to form blocks. This invention offers considerable savings oftime, energy and capital over current practices.

SUMMARY OF THE INVENTION

In accordance with the present invention, FACW or other liquidsubstances containing similar concentrations of ammonium lactate andtotal solids can be solidified by mixing it with certain calcium salts.Depending on the salt used and the conditions of addition, substantialamounts of heat can be generated. At elevated temperatures the FACW orammonium lactate-containing substance can be maintained as a liquid. Therate of solidification in turn can be regulated by controlling the rateand extent of cooling. For example, with calcium chloride, the mixturetypically begins to thicken at 25° to 30° C. and can solidify completelywithin an hour. The solidified product reaches maximum hardness afterone to several days. This hardening is not associated with evaporationof water, since it will occur in an air-tight package.

The invention is applicable to the manufacture of solid FACW in variousforms. In its raw form, it can be solidified in molds to form lickblocks or cubes, or it can be extruded to produce pellets or granules.The solidified material can be crushed to form a powder or it can be"shaved" to produce flakes.

Trace ingredients such as minerals, vitamins or drugs can also be addedto the FACW prior to processing. Substantial amounts of molasses, cornsteep liquid or other feed ingredient also may be added.

In accordance with the invention the aforesaid compositions may be usedto make animal feed products in which they bind products such as grains,roughage and forage materials into blocks, cubes or pellets. Thecompositions serve as excellent binding agents when blended in liquidform with those products and permitted to solidify. Typically suchmixtures will contain 20 to 40% FACW and 1 to 3% added calcium. Prior tosolidification the mixtures can be poured and/or compressed into rangeblocks or cubes or extruded to form pellets. The compressed mass canthen harden in twenty minutes or less. Unlike conventional binders thesecompositions are believed to serve to "cement" the solid productparticles rather than serving as a simple "adhesive". For this reasonthe application of excessive pressure is not required to achievesolidification.

MECHANISM OF SOLIDIFICATION

As previously described, FACW contains ammonium lactate as a primaryconstituent. It can exist as a solid, but since it is highly hydroscopicit remains liquefied under normal atmospheric conditions. The mechanismby which the FACW is solidified by the invention is not fullyunderstood. However, it is believed to involve the formation of calciumammonium lactate dihydrate (CAL), a solid crystalline substance. Aspresently understood, solvated calcium combines chemically with theammonium lactate in FACW, resulting in the production of the CAL saltwhich crystallizes and/or precipitates in mass to effect totalsolidification.

It has been found that in some cases, calcium ammonium lactate forms asa byproduct in the manufacture of FACW. The CAL sometimes deposits inmanufacturing equipment as a sediment, for example in pipes or storagevessels. This deposition can be prevented by removing calcium from thewhey used to make FACW. Such removal can be accomplished by ionexchange, prior to fermentation. A suitable ion exchange system is theresin Amberlite 200. Conversely, CAL can be obtained by purification ofFACW, i.e., by separating CAL crystals from FACW to obtain substantiallypure CAL.

Calcium ammonium lactate salt (CAL) has been synthesized in thelaboratory in the following manner: 500 parts by volume of the solutionin lactic acid is neutralized with 257 parts of aqueous ammonia (27.7%NH₃) and 5.55 parts by weight of Ca(OH)₂ or (1.1 parts CaCl₂.2H₂ O). Themixture is cooled to room temperature, pH adjusted to 6.8 with 1.0 NaOHsolution and diluted to 1 liter with water. After standing 4 to 7 days,well-formed crystals will form usually, however, seeding with CALcrystals and agitation may be necessary. The total crystal yield isapproximately 5% by weight of the prepared solution.

The chemical composition of the resulting salt is as follows:

    ______________________________________                                        Constituent          Percent.sup.1                                            ______________________________________                                        Calcium               8.6                                                     Ammonia Nitrogen as NH.sub.4                                                                        7.7                                                     Lactic Acid expressed as C.sub.3 H.sub.5 O.sub.3                                                   74.4                                                     Water                11.1                                                     Total                102.8                                                    ______________________________________                                         .sup.1 Average of 6 determinations.                                      

The empirical formula of the compound based on the above analytical datais Ca(NH₄)₂ (C₃ H₅ O₃)₄.2H₂ O. Unequivocal confirmation of thisempirical formula has not been made.

The crystalline solid is characterized by monolithic symmetry. Thecompound does not have a distinct melting point, but appears to losewaters of hydration at 120° C. and decompose at 190±5° C. CAL is verysoluble in water, slightly soluble in aqueous ammonia and insoluble inethanol. The solid has a specific gravity of 1.47.

Calcium ammonium lactate is useful in its own right as a feed supplementfor ruminant animals. CAL contains approximately 37.4 percent by mass ofcrude protein equivalent and the lactic acid constituent can serve as avaluable source of metabolizable energy. Calcium is an essential mineralof great nutritional importance. All of the constituents contained arevaluable sources of animal nutrition making CAL a concentrated feedsupplement that contains total feed value.

DETAILED DESCRIPTION

The present invention is applicable to FACW obtainable from varioustypes of whey and having a variety of compositions. FACW contains, asspecified in section #573.450 of the Federal Register, 35 to 55%ammonium lactate.

The calcium salts which are used in accordance with the invention aresalts of strong mineral acids, such as calcium chloride, calcium sulfateand calcium phosphate. Calcium chloride is preferred, being effective insmaller quantities, and producing harder products, than calcium sulfate,which in turn is more effective than calcium phosphate. Effectiveness isbelieved to be correlated with water solubility. It is possible also touse alkaline calcium salts such as calcium carbonate, calcium oxide orcalcium hydroxide. However, when alkaline calcium salts are used, amineral acid must be added in an amount sufficient to neutralize, sothat the FACW is not rendered alkaline, so as to prevent loss ofammonia. Preferably sufficient mineral acid is added to form the calciumsalt with all of the calcium.

The amount of calcium required to solidify an FACW-containing feed toany specified hardness generally has to be determined experimentally. Ithas been found that 6 to 10% calcium, by weight of FACW, is generallysufficient. This amount is the percentage of calcium. The amount of anyparticular calcium salt must be adjusted to give the appropriate amountof calcium.

The most elementary application of this invention is the solidificationof FACW. The FACW and calcium salt are mixed at room temperature todissolve the salt and the mixture poured into a suitable mold forhardening. It is best to slowly add this salt while vigorously mixingFACW to eliminate clumping and hasten its solution. If an alkalinecalcium salt is used in combination with mineral acids, as describedabove, the acids are best added to the FACW during agitation followed bythe slow addition of the alkaline salt. If calcium chloride (CaCl₂ ·2H₂O) is used singly or if mineral acids are added prior to the addition ofan alkaline salt, extensive heat is generated. Calcium chloride has apositive heat of solution and typically produces a temperature rise of1° to 1.5° C. (2° to 3° F.) for each percent of the dihydrate added.When mineral acids are used in combination with alkaline calcium salts,the heats generated result primarily from the solution of the acids. Theneutralization of the acidified FACW by the alkaline salt is notsignificantly exothermic. A rise of 1.5° C. (3° F.) is typicallyobserved for each percent of mineral acid (95% H₂ SO₄ or 85% H₃ PO₄)added.

The FACW-calcium mixture can be maintained as a free flowing liquid ifthe temperature is maintained above the temperature at whichsolidification is spontaneously initiated. This critical temperature istypically 25° to 30° C. but can vary depending on the exact compositionof the FACW, the calcium salt used, the amount of calcium added and therate of cooling. If the FACW prior to calcium addition is at roomtemperature (20° C.), the elevated temperatures obtained followingtypical additions of calcium chloride or mineral acids plus alkalinesalts is sufficiently high to maintain the FACW-calcium mixture in aliquid state. For example, if an FACW-calcium mixture is to contain 20%by mass of the dihydrate, with a temperature of 20° C. prior toblending, the temperature of the mixture will be typically 40° to 50° C.following complete solution of the calcium salts. Such a mixture willremain as a liquid for a prolonged period, unless it is cooled. If theadditions do not result in a mixture having a temperature that isgreater than the critical solidification temperature, sufficient heatmust be applied to the FACW fraction before blending to preventpremature solidification.

By regulating the rate and extent of cooling, the rate of solidificationcan be controlled. Relatively rapid solidification can result if thefluid is cooled at a specified rate to a temperature that nearly equalsor is slightly lower (supercooling) than the critical temperature beforebeing poured into a mold. Once the critical temperature is attained, theproduct can be maintained as a liquid for a period of approximately 2 to5 minutes, which is sufficient time to transfer the slightly thickenedfluid from the mixing vessel to the solidification mold. Oncesolidification is initiated, a hard, dry product can result in about 15minutes or less. The exact rate and extent of cooling employed whenapplying this method must be determined experimentally and will varywith the formulation used and the FACW composition. It is necessary tocontrol the rate of cooling so as to permit mold pouring at the criticaltemperature or during the supercooling phase. If cooling is too rapid,solidification can result prematurely and the method cannot be appliedto attain the desired result.

Rapid solidification is desired when insoluble materials such asminerals or grain fragments are slurried or suspended in liquid FACWprior to initiating the solidification process. When the process iscontrolled to produce rapid solidification the suspended material can behomogeneously distributed in the finished solid. This process isespecially applicable to the production of lick blocks containinginsoluble matter where the matter must be homogeneously suspended.

If the FACW mixture to be solidified contains no suspended solid matter,it may be desirable to implement a slow-setting procedure. Thisprocedure is simpler to employ, since careful regulation of the coolingrate is not necessary. The FACW-calcium mixture is simply maintained ata temperature that is greater than the solidification temperature,poured into an appropriate mold and permitted to cool (usually underambient conditions) until the solidification temperature is attained andsolidification is achieved. With this method, solidification usuallyoccurs in from 1 to 6 hours depending on the formulation used, theinitial temperature of the fluid and the cooling conditions. Generallythe temperature at which the fluid is poured should be at least 2° to 5°C. above the known solidification temperature so as to avoid prematuresolidification that could occur if pouring were attempted at a slightlylower temperature. If the temperature is more than 5° C. above the knownsolidification temperature, solidification will be delayed.

In addition to the production of solidified FACW in molds, thisinvention can be applied to the production of FACW pellets or cubesusing commonly known extrusion type devices. To apply these devices toliquid FACW-calcium mixtures at elevated temperatures, the mixtures mustbe cooled to the point at which solidification is initiated (orsupercooled) and forced through the extrusion device precisely when thedesired consistency is attained. When using such a process, the rate andextent of cooling have to be carefully regulated so that the material isthickened to a desirable consistency just prior to being forced throughthe die of the extrusion device. After it has been formed, the extrudedmaterial can harden completely within minutes. The exact timing must bedetermined by trial for each formulation used.

FACW solidification in accordance with the invention can be conductedalso with the inclusion of other nutrients, such as molasses, corn steepliquid, yeast extract products, minerals and vitamins. In addition,drugs added to feed products may be included depending on the final useof the product. For example, Rumensin® could be added to blocks, pelletsor cubes for feeding cattle. In general, larger amounts of calcium saltare needed to attain a desired hardness when the FACW contains excessiveamounts of molasses than when the process is practiced with FACW itself.Mixtures containing up to 25 parts by weight of molasses for each 100parts of FACW may be solidified using conventional amounts of thecalcium salts. Higher levels than 25 parts of molasses may be used, butthe level of calcium may have to be elevated. Other ingredients may alsoinfluence solidification, and trial and error must be implemented todetermine the level of calcium required to effect hardening.

A more sophisticated application of this invention is the use ofFACW-calcium mixtures to bind forage, roughage and other plant productswhen producing protein-concentrate pellets, cubes or range-blocks. It isbest to premix the FACW and calcium salt maintaining the temperaturehigh enough to prevent premature solidification, blend the resultingmixture with the ruminant animal feeds again maintaining an elevatedtemperature, and compress the blend in a mold or apply extrusion-typeprocessing. In such products it is generally desirable to include about30 to 40% by weight of the FACW-calcium salt mixture. The exact amountsof FACW and calcium required for solidification will vary with thenature of the ingredients included in the formulation, and the desiredhardness of the block. The exact formulation must be determinedexperimentally for each intended binding application.

When feeds of this type are produced using FACW, the regulation oftemperature during production is critical to the success of the process.Solidification of the FACW fraction must be prevented until the feedmixture is fully blended and compacted or extruded to its final shape bymaintaining it above the solidification temperature. If solidificationis premature, the ingredients will not bind adequately.

Generally if the liquid FACW-calcium premix and the plant ingredientsare blended rapidly and compressed or processed immediately, a wellbound product will result, even without auxiliary heating. Generally,when the liquid FACW-calcium mixture is at 40°-50° C., and it is blendedin normal proportions with the plant product mixture at roomtemperature, the temperature of the resulting blend is low enough toinitiate solidification of the FACW-calcium fraction. However, themixture generally will remain sufficiently moist and sticky to permitgood compaction to occur for a period of approximately 5 to 10 minutes.If the blended feed is to remain for an extended period of time beforecompression processing, the total feed must be heated so as to maintainit above the solidification temperature.

After blending the FACW, calcium salt and plant ingredients, the mixtureis compressed in the desired form and left to harden by thesolidification of the FACW. During formation sufficient pressing must beapplied to compact the product to a convenient density, i.e., removeextraneous pockets of air. If the solidified product is not to cure orbe stored in a mold, sufficient pressure must be applied to maintain theshape of the product until solidification is sufficiently complete toallow the shape to be maintained before the product is removed from themold.

The following examples illustrate the invention. All parts andpercentages are given on a weight basis, unless stated otherwise.

EXAMPLE I

The following formulation was used to produce a 30-pound lick-type rangeblock:

    ______________________________________                                        Ingredient       Percent                                                      ______________________________________                                        FACW (60% solids)                                                                              80                                                           CaCl.sub.2.2H.sub.2 O                                                                          20                                                                            100                                                          ______________________________________                                    

A 5-gallon bucket was used as a mixing vessel, with agitation from anair-driven barrel mixer fitted with a single set of three 2-inch blades.The mixing vessel was placed within a 15-gallon tub which was filledwith water for rapid cooling of the blended feed ingredients. The moldused to shape the lick block was a 3-gallon plastic tub (6×11×14inches). Utilization of the plastic tub permitted easy removal of thefinished block, since the inside walls were smooth and slightly taperedat the open end.

The CaCl₂.2H₂ O fraction (6 pounds) was poured slowly into thevigorously mixing FACW fraction (24 pounds). The mixture was agitatedfor approximately 5 minutes to assure complete solution of the addedsalt. After mixing, the temperature of the FACW mixture was elevated 33°C. from room temperature to approximately 56° C. After the initial 5minutes of mixing, cold tap water was circulated through the coolingvessel and the fluid cooled at an approximate rate of 1.5±0.5° C. perminute. The fluid mixture began to thicken when a temperature ofapproximately 31° C. was reached, and it was immediately poured into themold for solidification. The mixture hardened in about 10 minutes andwas removed from the mold after 1 hour. The block attained maximumhardness after two or three days of curing.

The finished block was chemically analyzed and observed to contain thefollowing:

    ______________________________________                                        Constituent         Percent (M/M)                                             ______________________________________                                        CPE                 36.9                                                      CPE from non-protein nitrogen                                                                     31.6                                                      Lactic acid         29.8                                                      Estimated solids    68.0                                                      Calcium             5.85                                                      ______________________________________                                    

This block was fed free-choice to a herd of heifers and dry cows undernormal field conditions and was observed to provide adequatepalatability and weatherability.

EXAMPLE II

A 30-pound lick-type block similar to that of Example I was preparedwith the inclusion of black strap molasses from the followingformulation:

    ______________________________________                                        Ingredient        Percent                                                     ______________________________________                                        FACW (60% solids) 70                                                          CaCl.sub.2.2H.sub.2 O                                                                           20                                                          Molasses, Black Strap                                                                           10                                                                            100                                                         ______________________________________                                    

The procedure used to produce this block was similar to that employed inExample I. The FACW and molasses were premixed, then the calcium saltwas added as previously described. This material required approximatelysix hours to solidify and several days to attain maximum hardness.

The finished block was chemically analyzed and observed to contain thefollowing:

    ______________________________________                                        Constituent          Percent                                                  ______________________________________                                        CPE                  33.3                                                     CPE from non-protein nitrogen                                                                      28.4                                                     Lactic acid          27.9                                                     Estimated solids     69.5                                                     Calcium              5.78                                                     ______________________________________                                    

This block when used in the field as a lick-feed was palatable andweathered well.

EXAMPLE III

The following formulation was used to produce a 30-pound FACW rangeblock using calcium carbonate plus acids for solidification:

    ______________________________________                                        Ingredients      Percent                                                      ______________________________________                                        FACW (60% solids)                                                                              68                                                           CaCO.sub.3       15                                                           85% H.sub.3 PO.sub.4                                                                           15                                                           95% H.sub.2 SO.sub.4                                                                           2                                                                             100                                                          ______________________________________                                    

In addition to neutralizing the alkaline effect of the carbonate, theacids served as a valuable source of phosphorus and sulfur.

This block was prepared using the apparatus described in Example I. Theacids were first added to the FACW and mixed. Following the addition ofthe acid, the temperature of the mixture rose from 23° C. to 48° C. TheCaCO₃ was next added slowly to the warm FACW-acid mixture over a periodof about 15 to 20 minutes. Extensive foaming, resulting from theproduction of carbon dioxide, was observed during and following theaddition of CaCO₃. Slow addition was used to control the neutralizationreaction and prevent excessive foaming. After carbonate addition wascompleted, the blend continued to produce gas slowly for periodsexceeding one hour.

After one hour, cooling was initiated. The liquid began to thicken whena temperature of about 27° C. was attained, and it was immediatelypoured into the mold.

Carbon dioxide production continued after the thickened liquid wastransferred to the molds, and the solidifying product expanded as theevolved gases were entrapped. The volume of the dried block was about50% larger than the freshly poured product. The product solidified inabout six hours and attained maximum hardness after several days ofcuring.

The finished block was chemically analyzed and found to contain thefollowing:

    ______________________________________                                        Constituent          Percent                                                  ______________________________________                                        CPE                  31.9                                                     CPE from non-protein nitrogen                                                                      27.5                                                     Lactic acid          26.2                                                     Estimated solids     70.5                                                     pH                   5.70                                                     Calcium              6.42                                                     Phosphorus           4.85                                                     Sulfur               0.52                                                     ______________________________________                                    

EXAMPLE IV

A 30-pound range block similar to that described in Example III wasproduced, with the inclusion of low moisture shelled corn, using thefollowing formula:

    ______________________________________                                        Ingredient       Percent                                                      ______________________________________                                        FACW (60% solids)                                                                              52.2                                                         CaCO.sub.3       12.0                                                         85% H.sub.3 PO.sub.4                                                                           12.0                                                         95% H.sub.2 SO.sub.4                                                                           1.6                                                          Ground corn, LMS 20.0                                                                          100                                                          ______________________________________                                    

The procedure implemented was similar to that described in Example III.The corn fraction was added to the other premixed ingredients just priorto initiating the cooling operation. A temperature rise of 22° C. wasobserved during preparation of the premix. Solidification was initiatedafter cooling to approximately 32° C. The thickening product was notpoured until it had attained a consistency that would permit suspensionof the corn fragments. The solidification was completed after about 6hours and maximum hardness was attained after several days of curing.The block matter was physically similar to that produced in Example III,and the corn particles appeared to be uniformly distributed within theproduct.

The finished product was observed to contain the following:

    ______________________________________                                        Constituent          Percent                                                  ______________________________________                                        CPE                  28.5                                                     CPE from non-protein nitrogen                                                                      22.6                                                     Lactic acid          22.3                                                     Estimated solids     74.0                                                     pH                   5.51                                                     Calcium              4.50                                                     Phosphorus           4.43                                                     Sulfur               0.26                                                     ______________________________________                                    

EXAMPLE V

A 200-gram high soy range cube was produced with FACW plus calciumserving as the binding agent using the following formulation:

    ______________________________________                                        Ingredient       Percent                                                      ______________________________________                                        Soybean meal     65.7                                                         FACW (60% solids)                                                                              28.1                                                         CaCl.sub.2.2H.sub.2 O                                                                          6.2                                                                           100                                                          ______________________________________                                    

The FACW and CaCl₂ ingredients were premixed with vigorous mechanicalagitation for about 5 minutes. This premix was then blended with thesoybean meal in a 500-liter stainless steel beaker using a large metalspatula. Blending was conducted for 3 to 5 minutes (just long enough toattain mixture uniformity) and immediately transferred to a 400-mlplastic beaker which served as a solidification mold. The blend wastightly packed by hand pressure, covered with plastic film and permittedto remain undisturbed for several hours before removing the mold. Themixing and packing operation employed in this example was sufficientlyrapid to avoid premature solidification. The product was sufficientlymoist and sticky at the time of packing to attain good binding.

The finished product was dry, observed to be of a desired hardness, anddisplayed good weathering characteristics. The finished product wasestimated to contain the following:

    ______________________________________                                        Constituent          Percent                                                  ______________________________________                                        CPE                  42.5                                                     CPE from non-protein nitrogen                                                                      9.9                                                      Lactic acid          10.1                                                     Estimated solids     80.1                                                     Calcium              1.90                                                     ______________________________________                                    

EXAMPLE VI

A 200-gram soy range cube similar to that described in Example V wasprepared with the inclusion of black strap molasses, using the followingformula:

    ______________________________________                                        Ingredient       Percent                                                      ______________________________________                                        Soybean Meal     59.1                                                         FACW (60% solids)                                                                              25.3                                                         Molasses, Black Strap                                                                          10.0                                                         CaCl.sub.2.2H.sub.2 O                                                                          5.6                                                                           100                                                          ______________________________________                                    

The preparation of this cube was similar to that produced in Example V.The molasses was premixed with the FACW prior to the addition of thecalcium salts. This product was also dry, observed to display desiredhardness and had good weathering characteristics. The finished productwas to contain the following:

    ______________________________________                                        Constituent          Percent                                                  ______________________________________                                        CPE                  38.5                                                     CPE from non-protein nitrogen                                                                      8.91                                                     Lactic acid          9.11                                                     Estimated solids     81.8                                                     Calcium              1.80                                                     ______________________________________                                    

EXAMPLE VII

Range blocks similar in composition to commercially produced proteinblocks were produced using FACW and CaCl₂ as binding agents in thefollowing three formulations:

    ______________________________________                                                        Percent                                                                         BLOCK    BLOCK    BLOCK                                     INGREDIENTS       1        2        3                                         ______________________________________                                        Soybean oil meal  47.9     40.4     30.3                                      FACW              26.7     32.8     41.1                                      Dehydrated alfalfa                                                                              9.20     9.20     9.20                                      Linseed meal      1.83     1.83     1.83                                      Calcium chloride, dihydrate                                                                     5.85     7.20     9.00                                      Ammonium polyphosphate                                                                          3.11     3.11     3.11                                      Ammonium sulfate   0.548    0.548    0.548                                    Sodium chloride   4.57     4.57     4.57                                      Zinc sulfate, heptahydrate                                                                       0.124    0.124    0.124                                    Manganese sulfate, monohydrate                                                                  .0496    .0496    .0496                                     Ferric sulfate    .0578    .0578    .0578                                     Magnesium sulfate, dihydrate                                                                     0.122    0.122    0.122                                    Cupric sulfate    .0952    .0952    .0952                                     Cobalt sulfate     .00194   .00194   .00194                                   Sodium iodide      .00066   .00066   .00066                                   Vitamins          #        #        #                                         TOTAL             100      100      400                                       ______________________________________                                    

#50,000 and 12,500 U.S.P. units of Vitamin A and Vitamin D₃,respectively, added per pound of block. The FACW and CaCl₂ componentswere premixed and added collectively to the remaining dry ingredients,which were also premixed. The FACW-CaCl₂ premixes were prepared in a2-gallon plastic bucket. Each FACW fraction was blended vigorously witha Grohav® air mixer fitted with a single set of 2-inch blades during theslow addition of each respective CaCl₂ fraction. Rapid mixing and slowaddition was used to prevent agglomeration and clumping of the CaCl₂.Each FACW-calcium premix was mixed for about five minutes after theaddition to assure that CaCl₂ had been totally dissolved. Thetemperature of each FACW fraction was elevated during the premixingoperations in which CaCl₂ was added. The temperature of the premixeswere elevated about 20° C. with the 22% additions of CaCl₂.2H₂ O.

The premixing of the dry ingredients was conducted in a Davis batchhorizontal ribbon-type mixer (Model #S-1) with a mixing capacity of fivecubic feet. The liquid premix was poured slowly and uniformly onto themixing dry ingredients to help assure uniformity of mix. After theliquid addition was completed, the mixing was continued for anadditional five minutes. Any feed that was sticking in excess to theribbon blades or remaining stagnant in the lower corners of the mixerwas then removed with a metal spatula and mixing was continued for anadditional five minutes.

Each of the blendings of feed ingredients mixed loosely and freely inthe horizontal ribbon mixer. The mixtures prepared to produce blocks 1and 2 (27 and 33% FACW, respectively) were moist and slightly sticky.The block 3 mixture (41% FACW) was noticeably more moist and sticky.Before solidification, the block 3 mixture was wet and almostpaste-like. Even though the three mixtures blended uniformly withoutclumping, they were observed to pack tightly if compressed in one'shand.

Excessive mixing times had to be avoided, since solidification of thefeed mixes initiated in about 15 minutes or less. If not removed fromthe mixer expeditiously, the mixtures were observed to form a hard,relatively dry crust on the back side of the ribbon blades and on themixer walls in areas of stagnant mixing. Also, if mixed excessively, thefeed mixtures were observed to dry to an extent that did not permitadequate packing, i.e., the feed particles lost their adhesive nature.

The moist, freshly-prepared feed blends were easily packed with gooduniformity into the block mold. Some disuniformity was observed in thedensity of the pack due to the layered addition of the feed mixture,i.e., the top portion of each strata was observed to be slightly moredense than the bottom portion. The moist feed materials prepared toproduce blocks 1 and 2 compressed to very firm solid masses that werenot easily crumbled. The block 3 mixture remained somewhat soft andpasty immediately after packing.

The feed mixtures were removed immediately from the mixer and packedinto a block solidification mold. The mold was a rectangular wooden box,constructed to approximate the shape and size of most commercial rangeblocks. The faces of the mold were held together by screws so as topermit the disassemblement of the box for easy removal of the finishedblock. The open end from which the mold was filled was filled with amovable lid that fit within the box. After filling, a 25-pound weightwas placed on the movable lid so as to apply a constant pressure to thesolidifying feed mixture.

Each feed mixture was packed manually in the solidification mold withthe butt end of a 4-foot length of 4×4" board weighing approximately tenpounds. The wet feed was added to the box in fractions weighing 1-2pounds each with each fraction being thoroughly tamped (packed) beforethe addition of each subsequent fraction. Once the mold was filled, thelid was placed on the exposed feed surface and weighed.

Even though the feed blends were left in the mold for 4 to 6 hours, itappears that blocks 1 and 2 would retain their shape and remain firm ifthe mold was removed immediately after packing. The blocks would likelymaintain some surface stickiness but would probably be resistant tocrumbling and breakage. After being compressed into the form of a block,they could be immediately packaged and stacked without being damaged.

The mold was removed from block 1 with little difficulty. The mold waseasily freed from the block mass with little resistance and little feedremained adhered to the wood. The block surface was dry and firm. Themold, however, was not easily removed from blocks 2 and 3. Considerableforce was needed to pull away from the wooden mold from block 2. Largefragments of the hardened feed adhered to the wood and were torn fromthe block. The block surface was still sticky but remained frim. Thisproblem possibly could have been alleviated if the mold were lined withsheet plastic or other non-stick surface prior to filling. Block 3adhered even more firmly to the wood mold. A metal spatula had to beforced between the block and the mold to release it. The block surfaceremained very sticky and although it was firm, an impression could bemade in it with the force of a person's thumb.

After being bagged and allowed to stand for a one-week curing period,all of the blocks were very hard and dry and displayed no surfacestickiness. The blocks as a whole were not easily crumbled, but somecrumbling was observed at the edges of the block surfaces.

Chemical analysis of the blocks provided the following information:

    ______________________________________                                        NUTRIENT          Block 1  Block 2  Block 3                                   ______________________________________                                        % Crude protein equivalent                                                                      39.5     38.1     36.3                                      % CPE derived from NPN                                                                          12.4     15.4     17.7                                      % Lactic acid     10.5     12.8     17.6                                      % Drymatter       83.8     81.7     78.3                                      pH                5.68     5.64     5.57                                      % Ash             12.1     12.8     15.4                                      % Calcium         1.64     2.13     2.37                                      % Phosphorus      0.91     0.69     0.71                                      % Sulfur          0.07     0.10     0.18                                      % Sodium          1.58     1.41     1.98                                      % Chloride        7.8      10       11                                        ______________________________________                                    

The blocks were fed and consumed by cattle in approximately the correctamount for their size and basal ratio. These blocks weathered well andwere judged to be equivalent to normal feed blocks.

This process is not restricted to these examples or devices but could becarried out using commercially available food and feed industryequipment by control of temperatures, FACW level and calcium level. Themolds used could be any commercially available container provided it wassufficiently rigid. Pressing of the material into the mold could be byany device such as cheese block presses or other such commonly useddevice. Feed block presses could also be used but high pressure is notrequired.

What is claimed is:
 1. The solid crystalline substance calcium ammoniumlactate dihydrate having monolithic symmetry.